Electrochemical fluorination of several methyl and/or ethyl esters of morpholino-substituted carboxylic acids

Article abstract of DOI:10.1016/S0022-1139(01)00443-2

Seven methyl and/or ethyl esters of carboxylic acids (-CH₂CH₂C(O)OEt, -CH₂CH₂CH₂C(O)OMe, -CH₂CH₂CH₂C(O)OEt, -CH(C₂H₅)C(O)OMe, -CH(n-C₃H₇)C(O)OMe, -CH₂CH₂CH₂CH₂C(O)OEt and -CH₂CH₂CH₂CH₂CH₂C(O) OEt) having a morpholino group were subjected to electrochemical fluorination (ECF). On ECF, the corresponding perfluoroacid fluorides bearing a perfluoromorpholino group were obtained in fair to good yields. Yields of the targeted perfluoromorpholino-containing perfluoroacid fluorides were influenced by the α-bond cleavage of the carboxylic acid and also by the kind of alkyl group of the carboxylic acid (the latter offering the possibility of cyclization side reactions). Perfluorooxolanes were formed as a major cyclization by-product from the ECF of morpholino-substituted carboxylic acids when the chain length of the alkyl group of the carboxylic acids had a carbon number of three or more and the structure of the alkyl group was branched in such a way as to allow cyclization. Perfluorodioxolanes were obtained in only small yields as the specific cyclization products when the ethyl esters of carboxylic acids were subjected to ECF. Spectroscopic data, as well as physicochemical properties, are described for the new perfluoroheterocyclic compounds with a perfluoromorpholino group that were produced.

Full text of DOI:10.1016/S0022-1139(01)00443-2

Journal of Fluorine Chemistry 111 ,2001) 115±128
Electrochemical ¯uorination of several methyl and/or ethyl
esters of morpholino-substituted carboxylic acids$
Takashi Abea,*, Hajime Babab, Kunio Okuharab, Haruhiko Fukayaa
aDepartment of Chemistry, National Industrial Research Institute of Nagoya, Hirate-cho 1-1, Kita-ku, Nagoya 462-8510, Japan
bDepartment for New Refrigerants Research, Research Institute of Innovative Technology for the Earth )RITE), c/o NIRIN,
Hirate-cho 1-1, Kita-ku, Nagoya 462-8510, Japan
Received 25 February 2001; accepted 15 June 2001
Abstract
Seven methyl and/or ethyl esters of carboxylic acids ,±CH2CH2C,O)OEt, ±CH2CH2CH2C,O)OMe, ±CH2CH2CH2C,O)OEt, ±
CH,C2H5)C,O)OMe, ±CH,n-C3H7)C,O)OMe, ±CH2CH2CH2CH2C,O)OEt and ±CH2CH2CH2CH2CH2C,O)OEt) having a morpholino
group were subjected to electrochemical ¯uorination ,ECF). On ECF, the corresponding per¯uoroacid ¯uorides bearing a
per¯uoromorpholino group were obtained in fair to good yields. Yields of the targeted per¯uoromorpholino-containing per¯uoroacid
¯uorides were in¯uenced by the a-bond cleavage of the carboxylic acid and also by the kind of alkyl group of the carboxylic acid ,the latter
offering the possibility of cyclization side reactions). Per¯uorooxolanes were formed as a major cyclization by-product from the ECF of
morpholino-substituted carboxylic acids when the chain length of the alkyl group of the carboxylic acids had a carbon number of three or
more and the structure of the alkyl group was branched in such a way as to allow cyclization. Per¯uorodioxolanes were obtained in only
small yields as the speci®c cyclization products when the ethyl esters of carboxylic acids were subjected to ECF. Spectroscopic data, as well
as physicochemical properties, are described for the new per¯uoroheterocyclic compounds with a per¯uoromorpholino group that were
produced. # 2001 Elsevier Science B.V. All rights reserved.
Keywords: Electrochemical ¯uorination; Per¯uoroacid ¯uorides; Per¯uoromorpholine; Per¯uorodioxolane; Per¯uorooxolane; Per¯uorooxane
1. Introduction
group, and have also shown that their yield was affected
by the type of dialkylamino- and alkyl groups of the
carboxylic acid skeleton [7±10]. We have already reported
on the ECF of several morpholino-substituted carboxylic
acids such as methyl morpholino-acetate [8], methyl 2-
morpholinopropionate [8], methyl 3-morpholinopropionate
[9], methyl 3-morpholino-2-methyl-propionate [10] and
methyl 3-morpholinobutyrate [10].
Per¯uorocarboxylic acids1 are versatile starting materials
for making agrochemicals, surfactants, polymers, etc [1,2].
Electrochemical ¯uorination ,ECF) of alkanoic carboxylic
acid derivatives ,esters, acid chlorides, acid ¯uorides) occu-
pies an important synthetic route in the industrial production
of per¯uorocarboxylic acids [3±6].
Previously, we have shown that the electrochemical ¯uor-
ination of methyl esters of N,N-dialkylamino-substituted
carboxylic acids gives various kinds of corresponding per-
¯uoroacid ¯uorides with a per¯uoro,N,N-dialkylamino)
As an extension of our work on the preparation of
N-containing per¯uorocarboxylic acids by means of ECF
[11], we have investigated the ECF of several hitherto
unexamined morpholino-substituted carboxylic acid alkyl
esters.
We report the results of the ECF of the following seven
carboxylic acid esters having a morpholino group ,1±7): c-
O,C2H4)2N±CH2CH2CH2C,O)OEt ,1), c-O,C2H4)2N±CH-
,C2H5)C,O)OMe ,2), c-O,C2H4)2N±CH2CH2CH2C,O)OMe
,3),c-O,C2H4)2N±CH2CH2C,O)OEt,4),c-O,C2H4)2N±CH2-
CH2CH2CH2C,O)OEt ,5), c-O,C2H4)2N±CH2CH2CH2CH2-
CH2C,O)OEt ,6), c-O,C2H4)2N±CH,n-C3H7)C,O)OMe
,7).
$ Electrochemical fluorination of N-containing carboxylic acids Part 9.
* Corresponding author. Present address: National Institute of Advanced
Industrial Science and Technology ,AIST), Research Center for Develop-
ing Fluorinated Greenhouse Gas Alternatives, AIST Tsukuba Central 5, 1-
1-1 Higashi, Tsukuba, Ibaraki 305-8565, Japan. Fax: ‡81-298-61-4771.
E-mail address: t.abe@aist.go.jp ,T. Abe).
1 The prefix `F' used in this paper designates ``perfluoro'' ,all C±H
bonds are replaced by C±F bonds).
0022-1139/01/$ ± see front matter # 2001 Elsevier Science B.V. All rights reserved.
PII: S 0 0 2 2 - 1 1 3 9 , 0 1 ) 0 0 4 4 3 - 2

116
T. Abe et al. / Journal of Fluorine Chemistry 111 )2001) 115±128
Scheme 1.
2. Results and discussion
with a bulky substituent like a morpholino group, has not
been conducted.
In previous papers, we have shown that there is a relation-
ship between the yield of mono-basic per¯uoroacid ¯uorides
from ECF and the structure of the substrate of the carboxylic
acid skeleton having an acyclic and/or a cyclic alkylamino
group [6,7]. For example, an increasing yield of per¯uor-
ocarboxylic acid ¯uorides was obtained by the comparative
study on the ECF of methyl esters of the corresponding
propionic acids ,substrates for 8 and 9) and butyric acids
,substrates for 10 and 11) with a morpholino group
,Scheme 1).
Yields were mainly affected by C±C and C±N bonds
scission from ECF, which in turn depended on the type of
,carbomethoxy) alkyl group of the substrates. Cyclization
took place as another side reaction in the case of methyl 3-
morpholino-butyrate, which gave per¯uoro,3-morpholi-
nooxolane) together with 10, as two of the major products
[10,11].
As far as ECF of the desired per¯uorocarboxylic acid
¯uorides with a per¯uoromorpholino group is concerned,
the best yield attained has been as high as 64% GC yield in
the case of per¯uoro,3-morpholino-2-methylpropionyl
¯uoride) ,11) from methyl 3-morpholino-2-methylpropio-
nate [10]. This led us to investigate whether or not there was
any correlation between the kinds of ¯uorination products
and the yield of the per¯uorocarboxylic acid ¯uorides when
other isomers of esters of butyric acids having a morpholino
group were subjected to ECF. It is known that cyclization
becomes a major reaction in the ECF of aliphatic carboxylic
acid derivatives ,acid halides and methyl esters) when the
chain length of the alkyl group is proper to form a 5- and a 6-
membered ring [12±14]. A systematic study of the ECF,
from the view point of the cyclization of carboxylic acids
We have ®rst undertaken the ECF of ethyl 4-morpholi-
nobutyrate ,1) and methyl 2-morpholinobutyrate ,2) in order
to compare the results with those of isomers like methyl 3-
morpholino-2-methylpropionate and methyl 3-morpholino-
butyrate [10].
When compound 1 was ¯uorinated ,Scheme 2), the corre-
sponding per¯uoro,4-morpholino-butyryl ¯uoride) ,12) was
obtained in a GC yield of 38.2% ,a yield between that of 9
,yield ˆ 17:1%) and 10 ,yield ˆ 43:2%) in Scheme 1).
Per¯uoro,N-propylmorpholine) ,13), which resulted from
the a-bond scission of the carboxylic acid, was formed as a
principal cleaved product as well. Although compound 1 has
a suf®cient number of carbon atoms in the alkyl group to
form an oxolane ring, the formation of per¯uoro,2-morpho-
linooxolane) ,14) [15], an expected cyclization product was
not detected. However, a small amount of another cycliza-
tion by-product ,assigned as per¯uoro[2-,3-morpholino-
propyl)dioxolane] ,15) from studying 19F NMR, MS, IR
and elemental analysis), were obtained.
It is known that ECF begins from those C±H bonds where
the electron density is relatively higher in the molecule on
the surface of the anodes [4±6,16,17]. In the case of 1, the
electron density at the CH2 group of the g-carbon of the alkyl
group of carboxylic acid is considered to be low due to the
presence of the N-atom at the d-position. To get information
about electron charges ,the lower the value, the higher the
electron density) on the alkyl group, computational calcula-
tions were carried out using the AM1 Hamiltonian for
compounds 1 and 5 and those having a protonated morpho-
line ring ,Fig. 1).
The results of the calculation show that in both protonated
cases, the electron density in the N-alkyl group is lowest at
Scheme 2.

T. Abe et al. / Journal of Fluorine Chemistry 111 )2001) 115±128
117
Fig. 1. The change of electron charges at the alkyl-group between non-protonated ,1 and 6) and protonated carboxylic acid esters with a morpholine ring.
stage of the ¯uorination. The intermediate compound, hav-
ing an oxetane ring, is considered too unstable, due to the
strain of the 4-membered ring compound during the ¯uor-
Scheme 3.
ination ,Scheme 4).
As far as charges at the CH2 group are concerned, com-
pound 5 has no barrier to formation of the reactive species on
the g-carbon at the early stage of ¯uorination Ð this leads to
the formation of per¯uoro[2-,morpholinomethyl)oxolane]
,16), through an intramolecular cyclization, as the ®nal
¯uorination product ,Scheme 7).
When 4-morpholinobutyric acid was ¯uorinated in the
form of the methyl ester ,3), the targeted 12 was similarly
obtained in comparable yield ,34.5%) as that obtained
from the ethyl ester 1, but without the formation of 15.
The formation of the latter cyclization product with a
per¯uorodioxolane was also con®rmed by the ECF of ethyl
3-morpholinopropionate ,4), from which corresponding per-
¯uoro,3-morpholinopropionyl ¯uoride) ,9) and the targe-
ted per¯uoro[2-,2-morpholinoethyl)dioxolane] ,18) were
formed in yields of 29.2 and 2.5%, respectively.
The formation of per¯uorodioxolanes from carboxylic
acid derivatives from ECF is not unprecedented. A Russian
patent has already been ®led for cyclization products
obtained by the ECF of ethyl esters of di-basic per¯uoro-
carboxylic acids [18]. It is considered that the formation of
the dioxolane ring is effected by the attack of reactive
species ,a radical and/or a radical cation) formed intramo-
lecularly on the ethoxy group towards the carbonyl carbon.
For example, compound 18 is considered to be formed from
4 ,as shown in Scheme 5).
Although various types of per¯uoroheterocyclic com-
pounds having two per¯uoroheterocyclic rings at the
o,o0-positions of a per¯uoromethylene group have been
reported, those having a per¯uorodioxolane and a per¯uor-
omorpholine have not yet been prepared [19±22]. A series of
a-position to the nitrogen. The value at the CH2 group
between non-protonated and protonated molecules changes
positively from 0.122 to 0.158 for 1, and from 0.123 to 0.161
for 5. Greater changes in electron charges were observed
at the a-CH2 group of the morpholine ring both for 1 and 5
,in which the values change from 0.060 and 0.056 to 0.143
and 0.148 for the former, and from 0.056 to 0.137 for the
latter). With respect to the charge at the b-position from the
nitrogen in the alkyl group of carboxylic acid ethyl esters,
greater changes were observed in the case of 1 ,varying from
0.004 to 0.066), while that of 5 showed only very small
changes ,varying only from 0.027 to 0.033).
When the electron density of the molecule is taken into
consideration, the C±H bonds a to the nitrogen, including
those at the ring and the N-alkyl group, are thought to be
¯uorinated at the last stage of ¯uorination, after the ECF of
other parts of the carboxylic acid group is complete. During
the course of ¯uorination, the initially ¯uorinated part of the
alkyl chain of the carboxylic acid group is considered to be
going to part from the surface of the anodes successively as
the ¯uorination proceeded because of the loss of basicity. It
is considered that it is the time gap, between ECF of the C±H
bond at the g-carbon ,a to the nitrogen) and the rest of the
carboxylic acid, that deprives 1 of a chance for the formation
of 14 and a bicyclic compound ,another possible cyclization
product shown in Scheme 3).
The formation of the 4-membered ring compound ,17) is
also possible as an another cyclization product from 1,
because that part of the molecule, including the b-CH2
group from the carbonyl group, is ¯uorinated at the same
Scheme 4.

118
T. Abe et al. / Journal of Fluorine Chemistry 111 )2001) 115±128
Scheme 5.
these new type of compounds, found to be formed in small
yields ,GC yield ˆ 0:9À2:5%) from the ECF of the ethyl
esters of linear alkyl carboxylic acids ,1, 4±6), was deter-
mined by the measurement of physicochemical properties
and spectral data. For example, mass spectra of these per-
¯uoroheterocyclic compounds characteristically show major
For example, it has been reported that the targeted per-
¯uoro,3-morpholinobutyryl ¯uoride) ,10) was obtained,
along with 20, by the ECF of methyl 3-morpholinobutyrate
in yields of 43.2 and 6.9%, respectively [10]. Compound 20
was also formed as the same by-product as a result of the
cyclization from ECF of 2.
In the ECF of 1, it is considered that the nitrogen atom of
the morpholino group in the substrate effectively acts to
block intramolecular cyclization [11]. Compound 1 ,through
cyclization at the side of the alkyl group of the carboxylic
acid) gave the targeted per¯uoroacid ¯uoride ,12) from ECF
as the principal products without the formation of any by-
products ,such as 14). Also of interest to us was the ECF of a
series of esters of morpholino-substituted carboxylic acids
Ð we wanted to investigate whether or not there was any
trend in cyclization of the alkyl group of the carboxylic acid
when the structure and the chain length of the alkyl group
were changed.
‡
fragment ions, such as [c-CF,OCF2)2] at m/e 163, [c-
‡
O,CF2CF2)2NCF2] at m/e 280 and an ion of [c-
‡
CF,OCF2)2,CF2)n] ,where n is the number of carbon atoms
of the alkyl group of the carboxylic acid substrate). In their
19F NMR spectra, an absorption peak due to ±CF at the 2-
position of the dioxolane ring shifts unusually to low ®eld ,j
À80.4 to À80.7 ppm) as a result of the deshielding by the
two adjacent oxygen atoms. In addition, two sets of geminal
¯uorines at the 4- and 5-position appear as an ABquartet
from j À84.8 to À84.9 ppm and j À87.0 to À87.1 ppm
with JAB ˆ 129 Hz.
When compound 2 was subjected to ECF, the targeted
per¯uoro,2-morpholinobutyryl ¯uoride) ,19) and per-
¯uoro,3-morpholinooxolane) ,20) ,rather than 13) were
obtained as the principal ¯uorination products, as shown
in Scheme 6.
The ECF study was thus extended to several other linear
alkyl-type carboxylic acids having a o-morpholino-alkyl
group such as ethyl 5-morpholinovalerate ,5) and ethyl 6-
morpholinohexanoate ,6).
The yield of the targeted per¯uoroacid ¯uoride ,19) was
low, apparently due to the occurrence of a cyclization side
reaction. We have shown that ECF of tertiary amines
bearing an R1,R2)N±CH,CH3)CH2C,O)OMe group gives
a per¯uorooxolane with a corresponding RF1,RF2)N-group
,RF1; RF2 ˆ perfluoroalkyl groups) at the 3-position [10,11].
When ethyl 5-morpholinovalerate ,5) was ¯uorinated, the
desired per¯uoro,5-morpholinovaleryl ¯uoride) ,21) was
formed in a yield of 32.5%, along with a per¯uorocy-
clic ether ,per¯uoro[2-,morpholinomethyl)oxolane] ,16),
yield ˆ 7:2%). Small quantity of per¯uoro[2-,4-morpholi-
nobutyl)dioxolane] ,22) were also obtained as another
cyclization product ,Scheme 7).
When ethyl 6-morpholinohexanoate ,6) was similarly
¯uorinated, the desired per¯uoro,6-morpholinohexanoyl
¯uoride) ,23) and per¯uoro[2-,2-morpholinoethyl)oxolane]
,24) were formed as major products, in yields of 27.0 and
14.0%, respectively. When compared with the results
obtained from the ECF of 5, the increase in the number
of bonds between the nitrogen atom of the morpholino
group and the CH2 group at the g-position of the carboxylic
acid of the substrate appears to have made it more easy for
Scheme 6.
Scheme 7.

T. Abe et al. / Journal of Fluorine Chemistry 111 )2001) 115±128
119
Scheme 8.
Scheme 9.
Scheme 10.
Fig. 2. 19F NMR of perfluoro,2-methyl-4-morpholinooxolane).

120
T. Abe et al. / Journal of Fluorine Chemistry 111 )2001) 115±128
Table 1
19F NMR spectral data of compounds 12, 15, 16, 19, 21±24, 26±29, 33, 34, 37, 39±43
Compound
Formula
Chemical shifta,b
J ,Hz)b
12
a À87.6 ,s)
b À92.7 ,m)
c À90.7 ,triple quintet)
d À124.3 ,m)
c À b ˆ 17.2, c À e ˆ 13.8
e À f ˆ eÀc ˆ 11.9±12.1
e À118.8 ,double triplet)
f 25.2 ,m)
15
a À87.6 ,s)
b À92.7 ,m)
JAB ˆ 190
c À91.1 ,triple quintet)
d À123.8 ,m)
e À125.9 ,m)
f À80.5 ,s)
c À b ˆ c À e ˆ 17.2
g À84.9, À87.0
JAB ˆ 128
JAB ˆ 194
16
a À87.7 ,s)
b À92.2, À92.8
c À88.5 ,m)
d À123.7 ,m)
e À127.4, À130.5
f À128.2, À135.8
g À83.5, À84.4
JAB ˆ 256
JAB ˆ 252
JAB ˆ 131
19
21
a À83.1, À88.4
b À84.8, À94.1
c À150.0 ,m)
d À79.3 ,d)
JAB ˆ150
JAB ˆ199
e À c ˆ 12.1
JAB ˆ 292
e À121.0, À122.7
f 25.5 ,d)
f À c ˆ 20.6
a À87.6 ,s)
b À92.7 ,m)
c À91.0 ,triple quintet)
d À123.5 ,m)
e À123.5 ,m)
f À118.7 ,m)
g 23.5 ,m)
c À b ˆ c À eˆ 15.5±17.2
JAB ˆ 248
JAB ˆ 248
22
23
24
a À87.6 ,s)
b À92.7 ,m)
c À90.9 ,triple quintet)
d À122.6 ,m)
e À124.0 ,m)
f À125.5 ,m)
g À80.4 ,m)
c À b ˆ c À e ˆ 17.2
h À84.8, À87.0
JAB ˆ 129
a À87.6 ,s)
b À92.8 ,m)
c À90.9 ,triple quintet)
d À122.4 ,m)
e À123.0 ,m)
f À123.9 ,m)
g À118.7 ,m)
h 25.2 ,m)
c À b ˆ c À e ˆ 17.9±18.9
a À87.6 ,s)
b À92.7 ,m)
c À89.6, À91.3
d À126.6, À136.6
e À124.3 ,m)
JAB ˆ 247
JAB ˆ 250
f À121.1, À125.7
g À128.1, À129.8
h À82.7, À84.6
JAB ˆ 193
JAB ˆ 257
JAB ˆ 130

T. Abe et al. / Journal of Fluorine Chemistry 111 )2001) 115±128
121
Table 1 ,Continued )
Compound
Formula
Chemical shifta,b
J ,Hz)b
26
a À87.6 ,s)
b À92.7 ,m)
c À90.9 ,triple-quintet)
d À122.2 ,m)
e À122.8 ,m)
f À123.8 ,m)
g À125.4 ,m)
h À80.4 ,m)
c À b ˆ c À e ˆ 15.5±18.9
i À84.8, À87.0
JAB ˆ 129
27
a À83.7, À88.3
b À84.8, À94.0
c À149.6 ,m)
d À81.6 ,t)
JAB ˆ 150
JAB ˆ 195
d À f ˆ 10.3
JAB ˆ 288
e À117.7 ,m)
f À122.9, À124.0
g 26.3 ,m)
28
a À84.8, À86.6
b À90.5, À91.5
c À133.8 ,m)
d À121.3
JAB ˆ 152
JAB ˆ 202
d À e ˆ JAB ˆ 260
e À107.1
f À125.0
g À80.1 ,d)
h À78.4
g À d ˆ 15.5
h À i ˆ JAB ˆ 137
i À69.3
28
a À85.1, À86.4
b À91.0 ,m)
c À137.3 ,m)
d À120.5
JAB ˆ 146
d À e ˆ JAB ˆ 262
e À122.7
f À129.2
g À81.6 ,d-d)
h À89.5
g À e ˆ 17.2, g À d ˆ 3.7
h À i ˆ JAB ˆ 138
i À69.3
29
a À84.9, À85.3
b À86.9, À88.3
c À152.8 ,m)
JAB ˆ 153
JAB ˆ 195
d À120.0, À133.5
e À124.9, À134.6
f À80.8, À92.7
g À76.5, À85.6
JAB ˆ 277
JAB ˆ 259
JAB ˆ 159
JAB ˆ 155
33
34
37
a À87.5 ,s)
b À92.6 ,m)
c À90.8 ,triple quintet)
d À124.5 ,quintet)
e À119.2 ,triplet)
f d 4.00
c À b ˆ c À e ˆ 14.7±17.2
d À b ˆ 12.1
e À cˆ 13.3
a À83.3, À88.4
b À85.0, À94.3
c À146.7 ,m)
d À79.1 ,d)
JAB ˆ 150
JAB ˆ 194
d À c ˆ 12.1
JAB ˆ290
e À120.3, À122.2
f d 3.50
a À87.6 ,s)
b À92.8 ,m)
c À91.1 ,double quintet)
d À127.1 ,quintet)
e À80.7 ,m)
c À e ˆ 11.0, c À b ˆ 17.2±18.9
d À b ˆ 10.2±12.1
f À84.9, À87.1
JAB ˆ 129

122
T. Abe et al. / Journal of Fluorine Chemistry 111 )2001) 115±128
Table 1 ,Continued )
Compound
Formula
Chemical shifta,b
J ,Hz)b
39
a À87.6 ,s)
b À92.7 ,m)
c À91.1 ,triple quintet)
d À124.8 ,m)
e À127.1 ,m)
f À81.5 ,t)
c À b ˆ c À eˆ 17.2
f À d ˆ 10.4
40
41
42
a À87.6 ,s)
b À92.7 ,m)
c À90.9 ,triple quintet)
d À123.6 to À123.8 ,m)
e À123.6 to À123.8 ,m)
f À119.0 ,t)
c À b ˆ c À e ˆ 15.5±18.9
f À d ˆ 12.1
g d 4.00
a À87.6 ,s)
b À92.7 ,m)
c À90.9 ,triple quintet)
d À123.7 ,m)
e À124.0 ,m)
f À126.7 ,m)
g À81.3 ,m)
c À b ˆ c À e ˆ 15.5±18.9
a À87.6 ,s)
b À92.7 ,m)
c À90.8 ,triple quintet)
d À122.6 ,m)
e À123.3 ,m)
f À123.9 ,m)
g À118.9 ,t)
h d 4.00
JAB ˆ 190
c À b ˆ c À e ˆ 17.2
g À e ˆ 11.9
43
a À83.9, À88.3
b À85.1, À94.2
c À147.1 ,m)
d À81.7 ,t)
JAB ˆ 142
JAB ˆ 203
d À f ˆ 10.4
JAB ˆ 299
e À122.8 ,m)
f À116.4, À117.5
g d 4.00
a
19F chemical shifts ,ppm) relative to internal CFCl3 ,negative shifts are upfield) and 1H chemical shifts ,ppm) relative to TMS.
b Only obvious chemical shifts and coupling constants are given.
intramolecular cyclization, increasing the amount of
formation of a cyclization product from 7.2% ,for 16)
to 14.0% ,for 24) ,Scheme 8).
tions on the same ring ,shifts occur to lower ®eld due to the
deshielding by the oxygen), appear at ca. j À83 and
À85 ppm with JAB ˆ 132À140 Hz and ca. j À78 and
À92 ppm with JAB ˆ 156À160 Hz, respectively [23±26].
The two isomers ,A and B) can thus be differentiated by
comparing chemical shifts and their coupling constants.
The 19F NMR of the compound 24, which was separated
from other components by GC, showed only one ABquartet
,j À82.7, À84.6 ppm, JAB ˆ 130 Hz) in the region of j
À80 to À95 ppm, other than peaks due to c-
O,CF2CF2)2NCF2±, which were assigned conclusively to
the vicinal ¯uorines at the 5-position of the per¯uoro,2-
alkyloxolanes) by comparing with the reported data for A
and B,see Table 1). Thus, it was revealed that the cyclic
ether obtained as the major component was only 24, with no
concomitant formation of isomeric 25.
It is known that per¯uorocyclic ethers, which were formed
together with targeted per¯uoroacid ¯uoride by the ECF of
aliphatic carboxylic acids, consist primarily of per¯uoro,2-
alkyloxolanes) ,A), with per¯uoro,2-alkyloxanes) ,B) pre-
sent in only small amounts [12±14]. The formation of an
isomeric per¯uoro[2-,morpholinomethyl)oxane] ,25),
besides 24, was similarly expected in the case of 6. Since
separation of a mixture of these cyclic ethers into each
isomer is known to be very dif®cult because of the close
similarity in physicochemical properties between the iso-
mers, detailed 19F NMR study was undertaken on the
per¯uorocyclic ether containing 24 ,puri®ed by means of
semi-preparative GC). The vicinal ¯uorines at the 5-position
of A and those at the 6-position of B, which are easily
distinguishable from other vicinal ¯uorines at other posi-
When methyl 2-morpholinovalerate ,7), an isomer of 5,
was ¯uorinated, the targeted per¯uoro,2-morpholinovaleryl

T. Abe et al. / Journal of Fluorine Chemistry 111 )2001) 115±128
123
¯uoride) ,27) and per¯uoro,2-methyl-4-morpholinooxo-
lane) ,28) were formed as the major products along with
per¯uoro,N-butylmorpholine) ,Scheme 9).
The formation of small quantities of per¯uoro,3-morpho-
linooxane) ,29), ,another, expected, 6-membered cyclized
compound), was also con®rmed. Although 19F NMR of 28
showed rather complex spectrum because of the mixture of
the two stereoisomers ,cis- and trans-isomers), their ratio
could be determined by studying the 19F NMR. The 19F
NMR spectrum of 28 is shown in Fig. 2.
morpholinopropionate ,4) was prepared by the Michael's
reaction of morpholine with ethyl acrylate.
The substrates synthesized for ¯uorination had the fol-
lowing boiling points: ethyl 3-morpholinobutylate ,1), bp
118±1208C/5 mmHg; methyl 2-morpholinovalerate ,2),
bp 1098C/5 mmHg; methyl 4-morpholinobutyrate ,3), bp
103±1048C/4 mmHg; ethyl 3-morpholinopropionate ,4),
137±1388C/22 mmHg; ethyl 5-morpholinovalerate ,5),
126±1278C/4 mmHg; ethyl 6-morpholinohexanoate ,6),
150±1538C/4 mmHg; methyl 2-morpholinovalerate ,7),
103±1048C/4 mmHg.
Previously, we reported the ECF of several 2-alkyl-sub-
stituted carboxylic acid methyl esters, which gave per-
Purity of anhydrous hydrogen ¯uoride ,AHF) ,Daikin
Industries Co.) was more than 99.9%. The electrolytic
¯uorination apparatus and operating procedures were simi-
lar to those described previously [3]. Analytical GLC work
was carried out with a Shimadzu GC-14Bgas chromato-
graph using stainless columns ,3 mm diameter) packed with
25% Fomblin YR on Chromosorb PAW ,6.4 m). For semi-
preparative work, a GASUKURO LL-75 modi®ed gas chro-
matograph using stainless columns ,10 mm diameter)
packed with 30% KelF wax on Chromosorb PAW
,4.9 m), and a Varian model 920 GC using an aluminum
column ,0.3/8 in. diameter) packed with 20% Fomblin YR
on Chromosorb PAW ,20 ft) were used. The carrier gas was
helium in all cases. Infrared spectra were measured on a
Shimadzu FTIR-8000PC spectrometer using a 6 cm gas cell
with KBr windows. 19F NMR spectra were measured on a
¯uoro,2,4-dialkyloxolanes) as
a cyclization product,
together with the corresponding per¯uoro,2-alkyl-substi-
tuted carboxylic acid ¯uorides) [27]. Determination of the
stereoisomeric structure of per¯uoro,2,4-dialkyloxolanes)
was achieved by comparative study of the 19F NMR both
of per¯uoro,2,4-dialkyloxolanes) and the corresponding
per¯uoro,2,5,5-trichloro-2,4-dialkyloxolanes)
prepared
from the former compounds by treating with an anhydrous
aluminum trichloride [28]. On the basis of the similarity of
the molecular structure between per¯uoro,2,4-dialkyloxo-
lanes) and per¯uoro,2-methyl-4-morpholinooxolane) ,28),
each of the stereo isomers of 28 was determined, based upon
information about the characteristic distinction between cis-
and trans-isomers in the 19F NMR spectra. For the two
absorption peaks due to the methine ¯uorine at the 4-
position, the peak which appeared characteristically at a
slightly lower ®eld ,j À133.8 ppm compared to j
À137.3 ppm), was assigned to the cis-form and the other
to the trans-form ,cis:trans-form ˆ 1:0.59).
Varian Unity Inova 300 spectrometer ,282.238 MHz for 19
F
1
and 299.95 MHz for H, respectively). Chemical shifts for
19F and 1H NMR spectra were reported relative to CFCl3 and
TMS, respectively. Positive shifts are down®eld from the
reference. MS spectra were measured on a Shimadzu GC/
MS-QP5000 and a Shimadzu GC/MS-QP1100EX instru-
ments ®tted with a capillary column ,Neutra Bond-1, 30 m
long, 0.25 mm i.d., 1.5 mm thick) at 70 eV. Elemental ana-
lyses were performed by Mikroanalytisches Labor Beller in
To check the stable conformation for 28, calculation of the
heat of formation of the cis- and trans-isomers was con-
ducted, using semi-empirical molecular orbital theory invol-
ving PM3 Hamiltonian ,Scheme 10).
Although the difference of heat of formation was very
small, it nevertheless suggested that the cis-form was
slightly more stable than the trans-form, in agreement with
the experimental results based on the 19F NMR.
È
Gottingen, Germany. Molecular orbital calculations were
conducted by a MOPAC program [30], and a CAChe system
,Sony Tektronix) was also used.
Our study on the preparation of new N-containing per-
¯uoroacid ¯uorides by means of ECF is in progress and
these results will be reported in due course.
3.1. Fluorination of ethyl 4-morpholinobutyrate )1)
Sample 1 ,40.9 g, 0.203 mol) was charged into a cell
containing 420 ml electrolytically puri®ed AHF, and the
solution was subjected to ¯uorination with an anodic current
density of 3.2 A/dm2, a cell voltage of 5.8±6.2 V, and a cell
temperature of 7±88C over a period of 610 min ,226 Ah). At
the ®nal stage of the ¯uorination, the voltage reached 6.2 V.
The ef¯uent gases from the cell were passed over NaF
pellets and then condensed in a trap cooled to À788C. The
gaseous products which did not condense in the À788C trap
were then bubbled through a ¯uoropolymer bottle contain-
ing water and a gas washing bottle containing an aqueous
solution of a mixture of K2CO3, KOH and KI. All products
except new ones were identi®ed by comparison of their
infrared spectra and GLC retention times with those of
3. Experimental details
Boiling points were uncorrected. Methyl or ethyl esters of
carboxylic acids with a morpholino group were prepared by
the reaction of morpholine with corresponding alkyl esters
of bromo-alkyl carboxylic acids [29]. Except for methyl 2-
bromovalerate which was used for the preparation of methyl
2-morpholinovalerate ,7), alkyl esters of bromo-alkyl car-
boxylic acids were commercially available and used as
received. Methyl 2-bromovalerate ,bp 83±878C/23 mmHg)
was prepared by the reaction of 2-bromovaleryl chloride ,bp
72±748C/27 mmHg) with methanol ,yield ˆ 98%). Ethyl 3-

124
T. Abe et al. / Journal of Fluorine Chemistry 111 )2001) 115±128
authenticated samples. New compounds were separated
from other products by use of semi-preparative GLC, and
an ice bath. The reaction took place immediately with an
evolution of heat giving a clear liquid. After shaking with an
addition of 1 ml water into the reaction mixture, the lower
phase ,methyl ester) was separated ,0.81 g, 87% yield).
Methyl per¯uoro,4-morpholinobutyrate) ,33) ,nc): bp
171.0±171.58C, d420 1.7379, n2D0 1.3202. IR ,capillary ®lm):
2970 n,CH) ,w), 1790 n,C=O) ,s), 1445 ,w), 1404 ,w), 1344
,s), 1292±1310 ,vs), 1219 ,vs), 1190 ,vs), 1167 ,vs), 1144
,vs), 1107 ,ms), 1084 ,ms), 1065 ,m), 968 ,m), 930 ,s), 818
their structures were determined on the basis of their IR, 19
F
NMR, MS spectra and elemental analysis ,carbon and
¯uorine).
The products ,7.0 g) condensed in the À788C trap con-
sisted of a mixture of per¯uoro,butyryl ¯uoride) ,30) and
per¯uoro,diethylether) ,31) ,2.9 g), per¯uoro,N-ethylmor-
pholine) ,32) ,1.8 g), per¯uoro,N-propylmorpholine) ,13)
,1.5 g) and unidenti®ed products ,0.8 g) ,products are
arranged in order of elution on GC). Cell drainings
,51.9 g) consisted of per¯uoro,N-propylmorpholine) ,13)
,9.0 g), per¯uoro,4-morpholinobutyryl ¯uoride) ,12)
,33.2 g), per¯uoro[2-,3-morpholinopropyl)dioxolane] ,15)
,2.6 g) and unidenti®ed products ,7.0 g). The GC yields of
per¯uoro,4-morpholinobutyryl ¯uoride) ,12) and per-
¯uoro[2-,3-morpholinopropyl)dioxolane] ,15) were 38.2
and 2.4%, respectively.
‡
,w), 779 ,m), 770 ,ms), 743 ,w). MS: 280 c-O,C2F4)2NCF2
‡
‡
,2.2), 214 C4F8N ,0.9), 209 CF2CF2CF2C,O)OMe ,4.6),
‡
‡
‡
181 C4F7 ,1.3), 169 C3F7 ,4.2), 164 C3F6N ,3.0), 150
‡
‡
‡
CF2CF2CF2 ,3.1), 147 C3F5O ,1.4), 145 C3F5O ,1.1),
‡
‡
‡
‡
131 C3F5 C3F5 ,2.9), 119 C2F5 ,21.5), 114 C2F4N
‡
‡
‡
,12.8), 109 CF2C,O)OMe ,1.1), 100 C2F4 ,22.9), 97
‡
‡
C2F3O ,1.5), 95 C2F3N ,1.4), 81 C3F3 ,4.1), 76
‡
‡
‡
C2F2N ,0.7), 69 CF3 ,15.2), 59 C,O)OCH3 ,100), 50
‡
CF2 ,3.3). Anal.: Calc. for C9F14NO3H3: C, 24.60; F, 60.59.
Found: C, 24.68; F, 60.8%.
Spectral data ,IR and MS) of per¯uoro,4-morpholinobu-
tyryl ¯uoride) ,12) and physicochemical properties and
spectral data of per¯uoro[2-,3-morpholinopropyl)-dioxo-
lane] ,15) are shown below. 19F NMR data of per¯uoro-
,4-morpholinobutyryl ¯uoride) ,12) and per¯uoro[2-,3-
morpholinopropyl)dioxolane] ,15) are shown in Table 1.
Per¯uoro,4-morpholinobutyryl ¯uoride) ,12) ,nc): IR
,gas): 1887 n,C=O) ,ms), 1346 ,m), 1310 ,s), 1295 ,s),
1238 ,vs), 1228 ,vs), 1210 ,m), 1195 ,m), 1179 ,s), 1153 ,s),
1133 ,m), 1107 ,m), 1046 ,w), 950 ,w), 932 ,m), 784 ,w),
19F NMR data of 33 are shown in Table 1.
3.2. Fluorination of methyl 2-morpholinobutyrate )2)
Sample 2 ,41.1 g, 0.220 mol) was ¯uorinated similarly
under the following conditions: 3.2 A/dm2, 5.9±6.5 V, 7±88C,
683 min ,253 Ah). Work-up gave the following products in
the À788C trap ,10.8 g): a mixture of per¯uoro,butyryl
¯uoride) ,30) and per¯uoro,diethylether) ,31) ,6.1 g), per-
¯uoro,N-propylmorpholine) ,13) ,3.0 g) and unidenti®ed
products ,1.7 g). Cell drainings ,66.6 g): per¯uoro,N-propyl-
morpholine) ,13) ,21.7 g), per¯uoro,2-morpholinobutyryl
¯uoride) ,19) ,18.9 g), per¯uoro,3-morpholinooxolane)
,20) [10] ,7.7 g) and unidenti®ed products ,7.5 g). The GC
yields of per¯uoro,2-morpholinobutyryl ¯uoride) ,19) and
per¯uoro,3-morpholinooxolane) ,20) were 20.1 and 8.2%,
respectively.
Spectral data ,IR and MS) of per¯uoro,2-morpholinobu-
tyryl ¯uoride) ,19) are shown below. 19F NMR data of
per¯uoro,2-morpholinobutyryl ¯uoride) ,19) are shown in
Table 1.
Per¯uoro,2-morpholinobutyryl ¯uoride) ,19) ,nc): IR
,gas): 1884 n,C=O) ,s), 1348 ,w), 1306 ,vs), 1286 ,s),
1200±1237 ,s±vs), 1196 ,s), 1176 ,s), 1152 ,s), 1099
,ms), 1020 ,w), 950 ,w), 934 ,m), 919 ,w), 878 ,w), 796
‡
776 ,w), 664 ,w). MS: 280 c-O,CF2CF2)2NCF2 ,60.1), 214
‡
‡
‡
C4F8N ,3.9), 197 CF2CF2CF2C,O)F ,7.4), 169 C3F7
‡
‡
,41.2), 164 C3F6N ,21.8), 145 C3F5N ,3.8), 142
‡
‡
‡
C3F4NO ,3.4), 131 C3F5 ,5.4), 119 C2F5 ,90.0), 114
‡
‡
‡
C2F4N ,78.8), 100 C2F4 ,90.0), 97 C2F3O ,5.9), 95
‡
‡
‡
‡
C2F3N ,4.2), 81 C3F3 ,3.1), 76 C2F2N ,3.6), 69 CF3
‡
,100), 50 CF2 ,17.0).
Per¯uoro[2-,3-morpholinopropyl)dioxolane] ,15) ,nc):
bp 161.5±162.08C, d420 1.8541, n2D0 1.3026. IR ,capillary
®lm): 1404 ,w), 1344 ,s), 1294±1310 ,s), 1140±1180 ,vs),
1220±1250 ,vs±s), 1101 ,s), 1084 ,ms, sh), 1069 ,ms), 1036
,w), 930 ,s), 846 ,w), 785 ,w), 762 ,s), 729 ,w), 702 ,w), 657
,ms).
‡
MS: 313 c-,CF2O)2CF±CF2CF2CF2 ,17.5), 311 c-
‡
‡
O,CF2CF2)2N±CF2CF ,14.5), 281 C6F11 ,3.9), 280 c-
‡
‡
‡
O,CF2CF2)2NCF2
,56.3), 214 C4F8N
‡
,1.7), 197
‡
‡
‡
‡
‡
‡
‡
CF2CF2CF2C,O)F ,7.8), 176 C4F6 ,2.2), 169 C3F7
,w), 760 ,w). MS: 380 [M À C,O)F] ,6.2), 308 C6F10O2N
‡
‡ ‡
,19.9). 164 C3F6N ,14.8), 163 c-,CF2O)2CF ,27.2),
,8.3), 242 C5F8NO ,2.2), 214 C4F8N ,13.0), 176 C4F6
,1.1), 169 C3F7 ,6.0), 164 C3F6N ,11.0), 145 C3F5N
‡
‡
‡
‡
‡ ‡
145 C3F5N ,6.6), 142 ,2.5), 131 C3F5 ,6.6), 119 C2F5
‡
‡
‡ ‡
,2.7), 142 C3F4NO ,4.0), 119 C2F5 ,100), 114 C2F4N
,100), 114 C2F4N ,46.9), 100 C2F4 ,63.3), 97 C2F3O
‡
‡
‡
‡ ‡ ‡
,13.2), 95 C2F3N ,1.1), 81 C3F3 ,2.3), 69 CF3 ,56.1), 50
‡
,26.1), 100 C2F4 ,51.9), 97 C2F3O ,6.5), 95 C2F3N ,3.5),
‡
‡
‡
‡
CF2 ,23.4). Anal.: Calc. for C10F18NO3: C, 22.90; F, 65.27.
Found: C, 22.76; F, 65.1%.
81 C3F3 ,1.9), 76 C2F2N ,4.2), 69 CF3 ,65.1), 50 CF2
,11.7).
Further characterization of per¯uoro,4-morpholinobu-
tyryl ¯uoride) ,12) was conducted in the form of the methyl
ester; into a 10 ml PFA resin bottle, was placed 0.899 g
,2.11 mmol) of 12 which was puri®ed by preparative GC,
and methanol ,0.48 g) was added dropwise while cooling in
Compound 19 was derivatized into the methyl ester ,34)
for further characterization as explained for 12 ,91% yield).
Spectral data ,IR and MS) of methyl per¯uoro,2-mor-
pholinobutyrate) ,34) are shown below. 19F NMR data of 34
are shown in Table 1.

T. Abe et al. / Journal of Fluorine Chemistry 111 )2001) 115±128
125
‡
‡
‡
Methyl per¯uoro,2-morpholinobutyrate) ,34) ,nc): bp
161.0±161.58C, d420 1.7431, n2D0 1.3211. IR ,capillary ®lm):
2968 n,CH) ,w), 1790 n,C=O) ,s), 1443 ,w), 1230 ,s), 1170±
1260 ,s, broad), 1165 ,s), 1142 ,s), 1126 ,s), 1094 ,m), 1082
,m), 1053 ,w), 976 ,m), 951 ,m), 930 ,s), 901 ,w), 810 ,w),
C3F6N ,12.5), 163 c-C2F4O2CF ,24.6), 150 C3F6 ,6.3),
‡
‡
‡
‡
147 CF2CF2C,O)F ,16.2), 145 C3F5N ,4.7), 119 C2F5
‡
‡
,100), 114 C2F4N ,42.3), 100 C2F4 ,58.1), 97 C2F3O
‡
‡
‡
,14.3), 95 C2F3N ,2.2), 81 C3F3 ,2.6), 69 CF3 ,45.6), 50
‡
CF2 ,21). Anal.: Calc. for C9F16NO3: C, 22.79; F, 64.14.
Found: C, 22.63; F, 64.3%.
‡
759 ,w), 746 ,w), 735 ,w). MS: 281 C6F11 ,3.0), 214
‡
‡
‡
‡
C4F8N ,10.1), 207 C5F7N ,9.6), 145 C3F5N ,4.2), 131
‡
‡
C3F5 ,7.9), 119 C2F5 ,33.5), 114 C2F4N ,7.9), 109
3.5. Fluorination of ethyl 5-morpholinovalerate )5)
‡
‡
‡
‡
‡
CF2C,O)OCH3 ,6.7), 100 C2F4 ,21.9), 97 C2F3O
‡
‡
,5.9), 95 C2F3N ,3.9), 81 C2F3 ,8.1), 73 C2FNO
‡
Sample 5 ,40.0 g, 0.186 mol) was ¯uorinated similarly
under the following conditions: 3.2 A/dm2, 5.8±6.1 V, 7±
88C, 633 min ,233 Ah). Work-up gave the following products
in the À788C trap ,7.7 g): a mixture of per¯uoro,diethylether)
,31), per¯uoro,valeryl ¯uoride) ,38) and per¯uoro,N-methyl-
morpholine) ,35) ,4.3 g), per¯uoro,N-ethylmorpholine) ,32)
,1.1 g), per¯uoro,N-propylmorpholine) ,13) ,1.4 g), per-
¯uoro,N-butylmorpholine) ,39) ,0.4 g) and unidenti®ed
products ,0.5 g). Cell drainings ,50.4 g): per¯uoro,N-butyl-
morpholine),39),8.5 g),per¯uoro[,2-morpholinomethyl)ox-
olane] ,16) ,6.4 g), per¯uoro,5-morpholinovaleryl ¯uoride)
,21) ,28.8 g), per¯uoro[2-,4-morpholinobutyl)dioxolane]
,22) ,1.0 g) and unidenti®ed products ,2.3 g). The GC yields
of per¯uoro[,2-morpholinomethyl)oxolane] ,16), per¯uoro-
,5-morpholinovaleryl ¯uoride) ,21) and per¯uoro[2-,4-
morpholinobutyl)dioxolane] ,22) were 7.2, 32.5 and 0.9%,
respectively.
Spectral data ,IR and MS) of per¯uoro,5-morpholinova-
leryl ¯uoride) ,21) and spectral data ,IR and MS) and
physicochemical properties of per¯uoro[,2-morpholino-
methyl)oxolane] ,16), per¯uoro[2-,4-morpholinobutyl)-
dioxolane] ,22) and per¯uoro,N-butylmorpholine) ,39)
are shown below. 19F NMR data of per¯uoro[,2-morpholi-
nomethyl)oxolane] ,16), per¯uoro,5-morpholinovaleryl
¯uoride) ,21) and per¯uoro[2-,4-morpholinobutyl)dioxo-
lane] ,22) and per¯uoro,N-butylmorpholine) ,39) are shown
in Table 1.
‡
,11.6), 69 CF3 ,32.5), 59 C,O)OCH3 ,100), 51 CF2H
‡
,6.7) 50 CF2 ,8.9). Anal.: Calc. for C9F14NO3H3: C, 24.60;
F, 60.59. Found: C, 24.60; F, 59.9%.
3.3. Fluorination of methyl 4-morpholinobutyrate )3)
Sample 3 ,41.1 g, 0.220 mol) was ¯uorinated similarly
under the following conditions: 3.2 A/dm2, 5.8±6.2 V,
7±88C, 608 min ,224 Ah). Work-up gave the following
products in the À788C trap ,8.7 g): a mixture of per¯uor-
o,butyryl ¯uoride) ,30) and per¯uoro,diethylether) ,31)
,4.8 g), per¯uoro,N-methylmorpholine) ,35) ,1.7 g), per-
¯uoro,N-ethylmorpholine) ,32) ,1.5 g) and unidenti®ed
products ,0.7 g). Cell drainings ,53.8 g): per¯uoro,N-pro-
pylmorpholine) ,13) ,11.4 g), per¯uoro,4-morpholinobu-
tyryl ¯uoride) ,12) ,32.4 g) and unidenti®ed products
,10.2 g). The GC yield of per¯uoro,4-morpholinobutyryl
¯uoride) ,12) was 34.5%.
3.4. Fluorination of ethyl 3-morpholinopropionate )4)
Sample 4 ,41.4 g, 0.221 mol) was ¯uorinated similarly
under the following conditions: 3.2 A/dm2, 5.8±6.2 V, 7±88C,
619 min ,230 Ah). Work-up gave the following products
in the À788C trap ,10.3 g): a mixture of per¯uoro,propionyl
¯uoride) ,36) and per¯uoro,diethylether) ,31) ,2.7 g),
per¯uoro,N-methylmorpholine) ,35) ,1.6 g), per¯uoro,N-
ethylmorpholine) ,32) ,4.6 g) and unidenti®ed products
,1.4 g). Cell drainings ,40.2 g): per¯uoro,N-ethylmorpho-
line) ,32) ,8.1 g), per¯uoro,3-morpholinopropionyl¯uoride)
,9) ,24.4 g), per¯uoro[2-,2-morpholinoethyl)dioxolane]
,37) ,2.7 g), and unidenti®ed products ,5.0 g). The GC
yields of per¯uoro,3-morpholinopropionyl¯uoride) ,9)
and per¯uoro[2-,2-morpholinoethyl)dioxolane] ,37) were
29.2 and 2.5%, respectively.
Per¯uoro,N-butylmorpholine) ,39) ,nc): bp 119.6±
120.28C, d420 1.8253, n2D0 1.2878. IR ,gas): 1887 ,ms),
1346 ,m), 1310 ,s), 1295 ,s), 1238 ,vs), 1228 ,vs), 1210
,m), 1195 ,m), 1179 ,s), 1153 ,s), 1133 ,m), 1107 ,m), 1046
,w), 950 ,w), 932 ,m), 784 ,w), 776 ,w), 664 ,w). MS: 314
‡
‡
‡
C6F12N ,1.1), 280 c-O,CF2CF2)2NCF2 ,24.5), 264
‡
‡
C5F10N ,6.8), 219 C4F9 ,15.1), 214 C4F8N ,1.2), 192
‡
‡
‡
C4F6NO ,1.6), 164 C3F6N ,13.8), 145 C3F5N ,2.3), 142
‡
‡
‡
C3F4NO ,1.8), 131 C3F5 ,16.0), 119 C2F5 ,89.3), 114
C2F4N ,53.6), 100 C2F4 ,68.4), 97 C2F3O ,5.1), 95
‡ ‡ ‡
Spectral data ,IR and MS) and physicochemical proper-
ties of per¯uoro[2-,2-morpholinoethyl)dioxolane] ,37) are
shown below. 19F NMR data of per¯uoro[2-,2-morpholi-
noethyl)dioxolane] ,37) are shown in Table 1.
‡
‡
‡
‡
C2F3N ,2.6), 81 C3F3 ,1.1), 76 C2F2N ,2.1), 69 CF3
‡
,100), 50 CF2 ,9.1). Anal.: Calc. for C8F17NO: C, 21.38; F,
71.94. Found: C, 21.30; F, 71.4%.
Per¯uoro[2-,2-morpholinoethyl)dioxolane] ,37) ,nc): bp
142.5±143.08C, d420 1.8312, [n2D0] 1.2986. IR ,capillary ®lm):
1344 ,s), 1292±1305 ,s), 1220±1250 ,vs±s), 1140±1170 ,vs),
1097 ,s), 1039 ,w), 982 ,ms), 930 ,s), 868 ,w), 789 ,w), 773
Per¯uoro[2-,morpholinomethyl)oxolane] ,16) ,nc): bp
133.5±134.08C, d420 1.8321, n2D0 1.2985. IR ,capillary ®lm):
1402 ,w), 1381 ,m), 1344 ,s), 1288±1305 ,s), 1217±1250
,vs±s), 1190 ,s), 1144±1170 ,vs), 1105 ,s, sh), 1078 ,vs),
991 ,ms), 930 ,s), 891 ,m), 808 ,w), 764 ,s), 738 ,w).
‡
,s), 735 ,w), 698 ,w). MS: 311 c-O,CF2CF2)2N±CF2CF
‡
‡
‡
‡
,6.0), 295 C6F11N ,2.3), 280 c-O,CF2CF2)2NCF2 ,43.7),
‡
MS: 458 [M À F] ,0.7), 292 C6F10NO ,2.9), 280
‡ ‡
‡
263 c-C2F4O2CF±CF2CF2 ,14.9), 176 C4F6 ,2.8), 164
c-O,CF2CF2)2NCF2 ,76.8), 247 C5F9O ,17.1), 219

126
T. Abe et al. / Journal of Fluorine Chemistry 111 )2001) 115±128
‡
‡
‡
‡
‡
C4F9 ,1.4), 197 C4F7O ,2.7), 192 C4F6NO ,2.5), 145
‡
7±88C, 594 min ,222 Ah). Work-up gave the following
products in the À788C trap ,10.4 g): a mixture of per¯uor-
o,diethylether) ,31), per¯uorobutyryl ¯uoride ,30) and
per¯uorovaleryl ¯uoride ,38) ,3.5 g), a mixture of per-
¯uoro,N-methylmorpholine) ,35), per¯uoro,N-ethylmor-
pholine) ,32) and per¯uoro,hexanoyl ¯uoride) ,3.0 g),
per¯uoro,N-propylmorpholine) ,13) ,1.6 g), per¯uoro,N-
butylmorpholine) ,39) ,0.6 g), per¯uoro,6-morpholinohex-
anoyl ¯uoride) ,23) ,0.3 g) and unidenti®ed products ,1.6 g).
Cell drainings ,52.0 g): per¯uoro,N-pentylmorpholine)
,41) ,8.6 g), per¯uoro[2-,2-morpholinoethyl)oxolane] ,24)
,13.0 g), per¯uoro,6-morpholinohexanoyl ¯uoride) ,23)
,25.1 g), per¯uoro[2-,5-morpholinopentyl)dioxolane] ,26)
,1.3 g) and unidenti®ed products ,4.0 g). GC yields of
per¯uoro[2-,2-morpholinoethyl)oxolane] ,24), per¯uoro,6-
morpholinohexanoyl ¯uoride) ,23) and per¯uoro[2-,5-mor-
pholinopentyl)dioxolane] ,26) were 14.0, 27.4 and 1.2%,
respectively.
Spectral data ,IR and MS) of per¯uoro,6-morpholinohex-
anoyl ¯uoride) ,23) and spectral data ,IR and MS) and
physicochemical properties of per¯uoro[2-,2-morpholi-
noethyl)oxolane] ,24), per¯uoro,N-pentylmorpholine) ,41)
and per¯uoro[2-,5-morpholinopentyl)dioxolane] ,26) are
shown below. 19F NMR data of per¯uoro,N-pentylmorpho-
line) ,41), per¯uoro[2-,2-morpholinoethyl)oxolane] ,24),
per¯uoro,6-morpholinohexanoyl ¯uoride) ,23) and per-
¯uoro[2-,5-morpholinopentyl)dioxolane] ,26) are shown
in Table 1.
‡
C3F5N ,3.3), 142 C3F4NO ,4.9), 131 C3F5 ,20.6), 119
‡
‡
C2F5 ,91.5), 114 C2F4N ,91.1), 100 C2F4 ,94.8), 97
‡
‡
‡
‡
C2F3O ,2.5), 95 C2F3N ,3.5), 81 C3F3 ,3.3), 76 C2F2N
‡
‡
,2.2), 69 CF3 ,100), 50 CF2 ,14.1). Anal.: Calc. for
C9F17NO2: C, 22.64; F, 67.72. Found: C, 22.26; F, 67.1%.
Per¯uoro,5-morpholinovaleryl ¯uoride) ,21) ,nc): IR
,capillary ®lm): 1884 n,C=O) ,ms), 1344 ,ms), 1305 ,s),
1292 ,s), 1200±1219 ,s±vs), 1192 ,s), 1171 ,vs), 1144 ,s),
1108 ,m), 1097 ,m), 1020 ,w), 930 ,ms), 885 ,w), 770 ,w),
‡
‡
‡
‡
756 ,w), 719 ,w). MS: 280 c-O,CF2CF2)2NCF2 ,56.5), 264
‡
‡
‡
‡
C5F10N ,3.8), 247 C5F9O ,4.6), 219 C4F9 ,11.8), 214
‡
C4F8N ,1.7), 192 C4F6NO ,2.1), 164 C3F6N ,18.7), 145
‡
C3F5N ,3.5), 142 C3F4NO ,3.5), 131 C3F5 ,2.9), 119
‡
‡
‡
C2F5 ,93.4), 114 C2F4N ,65.4), 100 C2F4 ,79.9), 97
‡
‡
‡
‡
C2F3O ,6.9), 95 C2F3N ,3.5), 81 C3F3 ,1.5), 76 C2F2N
‡
‡
,2.2), 69 CF3 ,100), 50 CF2 ,12.8).
Per¯uoro[2-,4-morpholinobutyl)dioxolane] ,22) ,nc): bp
178.5±179.08C, d420 1.8712, n2D0 1.3065. IR ,capillary ®lm):
1344 ,s), 1294±1310 ,s), 1200±1260 ,vs), 1140±1180 ,vs),
1097 ,s), 1016 ,w), 991 ,w), 930 ,w), 895 ,w), 849 ,w), 823
,w), 771 ,m), 754 ,ms), 727 ,w), 718 ,w), 660 ,m). MS: 574
‡
‡
[M À F] ,1.0), 436 C9F14O3N ,1.4), 363 [c-,CF2O)2CF±
‡
‡
CF2CF2CF2CF2] ,8.1), 342 c-O,CF2CF2)2NCF2CF2C
,4.2), 281 C6F11 ,2.4), 280 c-,CF2O)2NCF2 ,56.4), 247
‡
‡
‡
‡
‡
CF2CF2CF2CF2C,O)F ,2.6), 219 C4F9 ,11.7), 181 C4F7
‡
‡
,2.9), 169 C3F7 ,2.3), 164 C3F6N ,14.8), 163 [c-
‡
‡
‡
,CF2O)2NCF] ,25.1), 145 ,2.2), 131 ,21.2), 119 C2F5
‡
‡
,100), 114 C2F4N ,43.1), 100 C2F4 ,56.1), 97 C2F3O
Per¯uoro,N-pentylmorpholine) ,41): bp 138.5±139.08C,
d420 1.8438, n2D0 1.2922. IR ,capillary ®lm): 1344 ,s), 1294±
1308 ,s), 1217±1250 ,s±vs), 1190 ,s), 1171 ,vs), 1144 ,s),
1099 ,s), 1018 ,s), 989 ,w), 930 ,s), 880 ,m), 849 ,w), 777
‡
‡
‡
,13.5), 95 C2F3N ,2.1), 69 CF3 ,51.3), 50 CF2 ,18.4).
Anal.: Calc. for C10F18NO3: C, 22.90; F, 65.27. Found: C,
22.93; F, 66.0%.
Compound 21 was derivatized into the methyl ester ,40)
for further characterization as explained for 12 ,84% yield).
Methyl per¯uoro,5-morpholinovalerate) ,40) ,nc): bp
184.8±185.08C, d420 1.7571, n2D0 1.3210. IR ,capillary ®lm):
2968 n,C=O) ,w), 1790 n,C=O) ,s), 1445 ,w), 1345 ,w),
1292±1303 ,vs), 1217 ,vs), 1190 ,vs), 1167 ,vs), 1144 ,vs),
1097 ,s), 1034 ,w), 955 ,w), 930 ,s), 885 ,w), 814 ,w), 766
‡
,w), 766 ,w), 745 ,m), 719 ,ms). MS: 314 C6F12N ,3.7),
‡
‡
280 c-O,CF2CF2)2N±CF2 ,29.4), 192 C4F6NO ,1.3), 181
‡
‡
‡
‡
‡
C4F7 ,7.5), 164 C3F6N ,13.6), 145 C3F5N ,2.2), 142
‡
‡
C3F4NO ,1.9), 131 C3F5 ,9.1), 119 C2F5 ,94.3), 114
‡
‡
C2F4N ,52.8), 100 C2F4 ,57.2), 97 C2F3O ,5.0), 95
‡
‡
‡
‡
C2F3N ,2.0), 81 C3F3 ,1.0), 76 C2F2N ,1.6), 69 CF3
‡
,100), 50 CF2 ,6.9). Anal.: Calc. for C9F19NO: C, 21.64; F,
72.35. Found: C, 21.60; F, 72.5%.
‡
,w), 752 ,w). MS: 430 c-O,C2F4)2NCF2CF2CF2CF2 ,0.7),
‡
‡
342 C7F12NO ,1.6), 330 c-O,C2F4)2NCF2CF2 ,2.5), 281
‡
Per¯uoro[2-,2-morpholinoethyl)oxolane] ,24) ,nc): bp
154.3±154.88C, d420 1.8638, n2D0 1.3012. IR ,capillary ®lm):
1344 ,s), 1292±1310 ,s), 1200±1217 ,s±vs), 1158±1178 ,s±
vs), 1144 ,s), 1128 ,s, sh), 1099 ,s), 1078 ,s), 1013 ,m), 978
,m), 930 ,s), 868 ,w), 848 ,w), 837 ,w), 768 ,w), 748 ,m).
‡
C6F11
CF2CF2CF2CF2C,O)OMe ,10.1), 231 C5F9 ,1.9), 214
,2.0), 280 c-O,C2F4)2NCF2
‡
,13.3), 259
‡
‡
‡
‡
C4F8N ,1.5), 207 C5F7N ,2.4), 195 C4F7N ,1.5), 181
‡
‡
‡
‡
‡
C4F7 ,1.9), 176 C4F6 ,1.9), 169 C3F7 ,3.1), 164 C3F6N
‡
‡
‡ ‡
,9.4), 131 C3F5 ,11.2), 119 C2F5 ,45.1), 114 C2F4N
‡
MS: 297 C6F11O ,14.7), 280 c-O,CF2CF2)2N±CF2 ,72.9),
‡
‡
‡
‡
‡
,18.9), 100 C2F4 ,33.2), 97 C2F3O ,4.6), 81 C2F3 ,4.9),
‡
231 C5F9 ,1.7), 197 C4F7O ,5.8), 169 C3F7 ,24.8), 164
‡
‡
‡ ‡ ‡
‡
‡
‡
73 C2FNO ,3.7), 69 CF3 ,21.1), 59 C,O)OCH3 ,100), 50
‡
C3F6N ,20.5), 150 C3F6 ,4.3), 147 C3F5O , C2F5N2
‡ ‡
,4.8), 142 C3F4NO ,5.1), 131 C3F5 ,21.3), 119 C2F5
CF2 ,3.4). Anal.: Calc. for C10F16NO3H3: C, 24.54; F,
‡ ‡
62.17. Found: C, 25.24; F, 62.4%. 19F NMR data of 40 are
shown in Table 1.
,100), 114 C2F4N ,75.1), 100 C2F4 ,89.9), 97 C2F3O
‡ ‡ ‡
,2.5), 95 C2F3N ,3.0), 81 C3F3 ,2.2), 76 C2F2N ,2.0), 69
‡
‡
CF3 ,69.8), 50 CF2 ,9.4). Anal.: Calc. for C10F19NO2: C,
22.77; F, 68.50. Found: C, 22.71; F, 68.8%.
3.6. Fluorination of ethyl 6-morpholinohexanoate )6)
Per¯uoro,6-morpholinohexanoyl ¯uoride) ,23) ,nc): IR
,capillary ®lm): 1882 n,C=O) ,ms), 1344 ,ms), 1306 ,s),
1292 ,s), 1217 ,vs), 1190 ,s), 1171 ,vs), 1144 ,s), 1101 ,ms),
Sample 6 ,40.5 g, 0.177 mol) was ¯uorinated similarly
under the following conditions: 3.2 A/dm2, 5.7±6.0 V,

T. Abe et al. / Journal of Fluorine Chemistry 111 )2001) 115±128
127
1076 ,m), 1055 ,w), 978 ,w), 930 ,ms), 862 ,w), 770 ,w),
‡
¯uoro,3-morpholinooxane) ,29) were 18.3, 12.3 and
3.2%, respectively.
766 ,w), 746 ,w), 733 ,w). MS: 392 C8F14NO ,1.2), 314
‡
‡
‡
C6F12N ,2.4), 281 C6F11 ,1.8), 280 c-O,CF2CF2)2NCF2
‡
Spectral data ,IR and MS) of per¯uoro,2-morpholinova-
leryl ¯uoride) ,27) and spectral data ,IR and MS) and
physicochemical properties of per¯uoro,2-methyl-4-mor-
pholinooxolane) ,28) and per¯uoro,3-morpholinooxane)
,29) are shown below. 19F NMR data of per¯uoro,2-mor-
pholinovaleryl ¯uoride) ,27), per¯uoro,2-methyl-4-mor-
pholinooxolane) ,28) and per¯uoro,3-morpholinooxane)
,29) are shown in Table 1.
‡
‡
,63.5), 269 C5F11 ,2.3), 181 C4F7 ,8.2), 169 C3F7 ,3.7),
‡
‡
‡
164 C3F6N ,16.4), 145 C3F5N ,3.2), 142 C3F4NO ,3.8),
‡
‡
‡
131 C3F5 ,19.8), 119 C2F5 ,100), 114 C2F4N ,61.5),
‡
‡
‡
100 C2F4 ,72.5), 97 C2F3O ,7.6), 95 C2F3N ,2.2), 81
‡
‡
‡
‡
C3F3 ,1.8), 76 C2F2N ,1.8), 69 CF3 ,94.3), 50 CF2
,10.3).
Per¯uoro[2-,5-morpholinopentyl)dioxolane] ,26) ,nc):
bp 193.5±194.08C, n2D0 1.3061. IR ,capillary ®lm): 1344
,s), 1294±1310 ,s), 1200±1217 ,s±vs), 1140±1165 ,s±vs),
1101 ,s), 1074 ,m), 1034 ,w), 930 ,s), 820 ,w), 677 ,w), 748
Per¯uoro,2-morpholinovaleryl ¯uoride) ,27) ,nc): IR
,capillary ®lm): 1882 n,C=O) ,m), 1340±1350 ,m), 1285±
1303 ,s), 1200±1221 ,s±s), 1165 ,s), 1144 ,s), 1103 ,m, sh),
1084 ,m, sh), 1059 ,w), 993 ,w), 930 ,m), 881 ,w), 781 ,w),
‡
,w), 727 ,w). MS: 413 c-C2F4O2CFCF2CF2CF2CF2CF2
‡
‡
‡
,9.3), 281 C6F11 ,5.7), 280 c-O,CF2CF2)2NCF2 ,66.3),
‡
760 ,w), 723 ,w). MS: 429 [M À C,O)F] ,3.9), 308 ,9.7),
‡
‡
‡ ‡
269 C5F11 ,3.8), 197 C4F7O ,1.8), 191C4F7 ,5.6), 169
‡
292 C6F10NO ,4.5), 280 c-O,C2F4)2NCF2 ,3.7), 264
C5F10N ,7.5), 245 C5F9N ,2.3), 176 C4F6 ,2.4), 164
‡
‡
‡ ‡ ‡
C3F7 ,2.2), 164 C3F6N ,13.7), 163 c-C2F4O2CF ,35.2),
‡
‡
‡
‡ ‡ ‡
C3F6N ,7.7), 142 C3F4NO ,6.1), 131 C3F5 ,6.2), 119
145 C3F5N ,3.0), 131 C3F5N ,16.7), 119 C2F5 ,100),
‡
‡
‡
‡ ‡ ‡
114 C2F4N ,42.4), 100 C2F4 ,59.6), 97 C2F3O ,12.7), 69
‡
C2F5 ,100), 114 C2F4N ,22.3), 100 C2F4 ,46.3), 97
‡
‡
‡
‡
‡
CF3 ,56.9), 50 CF2 ,18.7). Anal.: Calc. for C12F22NO3: C,
23.08; F, 66.99. Found: C, 22.95; F, 67.0%.
C2F3O ,4.3), 95 C2F3N ,1.5), 76 C2F2N ,4.8), 69 CF3
‡
,74.8), 50 CF2 ,9.2).
Compound 23 was derivatized into the methyl ester ,42)
for further characterization as explained for 12 ,76% yield).
Methyl per¯uoro,6-morpholinohexanoate) ,42) ,nc): bp
200.5±201.08C, d420 1.7742, n2D0 1.3213. IR ,capillary ®lm):
2968 n,CH) ,w), 1790 n,C=O) ,s), 1445 ,w), 1402 ,w), 1345
,ms), 1292±1305 ,vs), 1169 ,vs), 1144 ,s), 1101 ,ms),
1084 ,m), 1000 ,w), 984 ,w), 930 ,s), 866 ,w), 843 ,w),
808 ,w), 754 ,w), 729 ,w), 714 ,w). MS: 309
Per¯uoro,2-methyl-4-morpholinooxolane) ,28) ,nc): bp
140.5±141.08C, d420 1.8778, n2D0 1.3044. IR ,gas):1360 ,w),
1311 ,m), 1287 ,m), 1265 ,s), 1231 ,vs), 1185 ,s), 1153 ,s),
1140 ,m, sh), 1117 ,s), 1085 ,m), 1063 ,w), 1002 ,w), 919
‡
,w), 875 ,w), 729 ,ms). MS: 458 [M À F] ,3.0), 411
‡
‡
‡
[M À C,O)F2] ,5.7), 345 c-O,CF2CF2)2NC2F5 ,3.5),
‡
342 c-O,CF2CF2)2NC2F5 ,4.2), 292 C6F10NO ,5.9),
262 C6F10 ,9.8), 181 C4F7 ,5.9), 176 C4F6 ,8.4), 169
‡
‡
‡
‡
‡
‡ ‡ ‡
CF2CF2CF2CF2CF2C,O)OMe ,0.7), 281 C6F11 ,1.0),
‡
C3F7 ,3.2), 164 C3F6N ,7.0), 150 C3F6 ,27.0), 145
‡
‡
‡ ‡ ‡
C3F5N ,8.9), 142 C3F4NO ,3.4), 131 C3F5 ,17.9), 119
280 c-O,C2F4)2NCF2 ,2.6), 231 C5F9 ,0.6), 219 C4F9
‡
‡
‡
‡ ‡ ‡
,0.5), 169 C3F7 ,0.7), 164 C3F6N ,2.0), 145 C3F5N ,0.9),
‡
C2F5 ,100), 114 C2F4N ,15.0), 100 C2F4 ,95.9), 97
‡
‡
‡ ‡ ‡
C2F3O ,15.2), 95 C2F3N ,9.9), 81 C3F3 ,2.8), 76
131 C3F5 ,9.7), 119 C2F5 ,19.7), 114 C2F4N ,10.2), 109
‡
‡
‡
‡
‡
‡
CF2C,O)OMe ,1.0), 100 C2F4 ,18.0), 97 C2F3O ,1.5),
‡
C2F2N ,5.1), 69 CF3 ,93.3), 50 CF2 ,12.7). Anal.: Calc.
for C9F174NO2: C, 22.64; F, 67.72. Found: C, 22.62; F,
66.8%.
‡
‡
81 C3F3 ,2.6), 69 CF3 ,16.0), 59 C,O)OCH3 ,100), 50
‡
CF2 ,2.1). Anal.: Calc. for C11F18NO3H3: C, 24.49; F,
63.45. Found: C, 24.60; F, 63.4%. 19F NMR data of 42 are
shown in Table 2.
Per¯uoro,3-morpholinooxane) ,29) ,nc): IR ,capillary
®lm): 1854 ,m), 1302 ,s), 1280 ,s), 1173±1260 ,s, broad),
1105±1135 ,s±vs), 1082 ,m), 1036 ,m), 997 ,s), 966 ,w), 935
,m), 923 ,m), 893 ,w), 764 ,m), 741 ,w), 715 ,w). MS: 457
3.7. Fluorination of methyl 2-morpholinovalerate )7)
‡
‡
‡
[M À F] ,1.7), 342 C7F11NO ,4.7), 312 C7F12 ,4.4), 311
‡ ‡
Sample 7 ,40.0 g, 0.199 mol) was ¯uorinated similarly
under the following conditions: 3.2 A/dm2, 5.8±6.1 V, 7±88C,
643 min ,234 Ah). Work-up gave the following products in
the À788C trap ,6.4 g): a mixture of per¯uoro,diethylether)
,31) and per¯uoro,propionyl ¯uoride) ,2.5 g), per¯uoro,bu-
tyryl ¯uoride) ,30) ,1.5 g), per¯uoro,N-methylmorpholine)
,35) ,1.0 g), per¯uoro,N-ethylmorpholine) ,32) ,0.7 g),
per¯uoro,N-butylmorpholine) ,39) ,0.4 g) and unidenti®ed
products ,0.4 g). Cell drainings ,59.1 g): per¯uoro,N-butyl-
morpholine) ,39) ,22.7 g), per¯uoro,2-morpholinovaleryl
¯uoride) ,27) ,17.3 g), per¯uoro,2-methyl-4-morpho-
linooxolane) ,28) ,11.6 g), per¯uoro,3-morpholinooxane)
,29) ,3.0 g) and unidenti®ed products ,4.4 g). The GC
yields of per¯uoro,2-morpholinovaleryl ¯uoride) ,27),
per¯uoro,2-methyl-4-morpholinooxolane) ,28) and per-
,54.3), 292 C6F10NO ,2.1), 264 C5F10N ,2.4), 247
C5F9O ,3.2), 195 C4F7N ,8.0), 150 C3F6 ,9.1), 145
‡
‡
‡
‡
‡
‡
‡
‡
‡
‡
C3F5N ,33.8), 131 C3F5 ,27.8), 119 C2F5 ,90.2), 114
C2F4N ,14.4), 100 C2F4 ,100), 97 C2F3O ,11.9), 95
‡
‡
C2F3N ,4.2), 93 ,4.6), 81 C3F3 ,2.9), 76 C2F2N ,4.7), 69
‡
‡
CF3 ,76.5), 50 CF2 ,12.9).
Compound 27 was derivatized into the methyl ester ,43)
for further characterization as explained for 17 ,88% yield).
Methyl per¯uoro,2-morpholinovalerate) ,43) ,nc): bp
175.5±176.08C, d420 1.7579, n2D0 1.3211. IR ,capillary ®lm):
2968 n,CH) ,w), 1790 n,C=O) ,s), 1443 ,w), 1302 ,s), 1280
,s), 1221±1270 ,vs±s), 1165±1200 ,s, broad), 1142 ,s), 1082
,m), 1055 ,w), 1026 ,w), 930 ,m), 881 ,w), 804 ,w), 789 ,w),
‡
745 ,m), 719 ,w). MS: 430 c-O,C2F4)2NCF,CF2CF2CF3)
‡
‡
,1.0), 342 C7F11NO ,0.7), 292 C6F10NO ,1.4), 264

128
T. Abe et al. / Journal of Fluorine Chemistry 111 )2001) 115±128
‡
‡
‡
‡
‡
[8] T. Abe, E. Hayashi, H. Fukaya, H. Baba, J. Fluorine Chem. 50 ,1990)
173±196.
C4F10N ,3.8), 231 C6F11 ,2.6), 181 C4F7 ,2.4), 176
‡
‡
C4F6 ,3.0), 169 C3F7 ,3.2), 164 C3F6N ,2.5), 145
‡
[9] T. Abe, E. Hayashi, H. Fukaya, Y. Hayakawa, H. Baba, S. Ishikawa,
K. Asahino, J. Fluorine Chem. 57 ,1992) 101±111.
[10] T. Abe, H. Fukaya, E. Hayashi, Y. Hayakawa, M. Nishida, H. Baba, J.
Fluorine Chem. 66 ,1994) 193±202.
‡
C3F5N ,3.1), 131 C3F5 ,5.5), 119 C2F5 ,34.4), 114
‡
‡
‡
‡
‡
C2F4N ,4.4), 109 CF2C,O)OCH3 ,6.6), 100 C2F4
‡
‡
,19.2), 97 C2F3O ,3.0), 95 C2F3N ,1.5), 81 C3F3
‡
‡
[11] T. Abe, H. Baba, I. Soloshonok, Electrochemical Fluorination of N-
containing Carboxylic Acids, Part 8; J. Fluorine Chem. 108 ,2001)
215±228.
,6.1), 76 C2F2N ,2.4), 69 CF3 ,25.6), 59 C,O)OCH3
‡
,100), 50 CF2 ,3.1). Anal.: Calc. for C10F16NO3H3: C,
24.54; F, 62.17. Found: C, 24.70; F, 62.4%. 19F NMR data of
43 are shown in Table 1.
[12] E.A. Kauck, J.H. Simons, US Patent 2644823 ,1953); Br. Patent
718318 ,1954).
[13] A.J. Rudge, Electrochemical fluorination, in: A.T. Kuhn ,Ed.),
Industrial Electrochemical Process, Elsevier, Amsterdam, 1971,
pp. 77±88.
Acknowledgements
[14] T. Abe, The synthesis of perfluoroethers by the electrolytic method,
in: Proceedings of the First Chinese±Japanese Seminar on Fluorine
Chemistry, 1±26 ,Tokyo), 12 October 1987, ,Abstract no. VII).
[15] I.P. Kolenko, N.A. Ryabinin, Tr. Inst. Khim. Ural., Nauchn. Tsentr.
Akad. Nauk. SSSR 28 ,1974) 60±65; Chemical Abstract 83 ,1975)
28030x.
This investigation was supported by the New Energy and
Industrial Technology Development Organization ,NEDO).
Authors wish also thank to Ms. J. Tachibana for taking
NMR, Mass and IR spectra.
[16] G.P. Gambaretto, M. Napoli, C. Fraccaro, L. Conte, J. Fluorine
Chem. 19 ,1982) 427±436.
[17] S. RuÈdiger, A. Dimitov, K. Hottmann, J. Fluorine Chem. 76 ,1996)
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